JPH0551386A - Spiro pyridopyran compound and guanine indicator using the same - Google Patents

Abstract

PURPOSE:A new compound useful for a guanine indicator, etc. CONSTITUTION:A compound of formula I [R<1>, R<2> are alkyl; R<3> is (substituted) alkyl; R<4> is H, alkyl, acyl; =X-is :=H-. =N-; Y is O. S; A is (substituted) hydrocarbyl aromatic ring], e.g. a compound of formula II. The compound of formula I is obtained by reacting a compound of formula III (X<-> is monovalent anion) with a compound of formula IV in a solvent such as methyl chloride or chloroform at -20 to 100 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel spiropyridopyran compound and a guanine indicator using the same. More specifically, the present invention relates to a novel spiropyridopyran compound that selectively recognizes a guanine derivative and develops a color, and a guanine indicator using the same.

[0002]

2. Description of the Related Art Conventionally, a compound which selectively recognizes a guanine derivative and develops a color has already been known, and these compounds are used as a guanine indicator.

[0003]

In various industrial fields, it is always desired to develop new compounds that have never existed as functional compounds.

The present invention relates to a guanine derivative, which is a compound which can be effectively used as a guanine indicator capable of selectively recognizing the guanine derivative to develop a color.
It is an object of the present invention to provide a novel spiropyridopyran compound having a chemical structure different from that of conventionally known compounds.

[0005]

Means and Actions for Solving the Problems The spiropyridopyran compound according to claim 1 is represented by the following general formula [I].

[0006]

[Chemical 2]

(Wherein R ¹ and R ² represent an alkyl group,
R ³ represents an alkyl group which may have a substituent, and R ^3
4 represents a hydrogen atom, an alkyl group or an acyl group, and = X-
Represents = CH- or = N-, Y represents an oxygen atom or a sulfur atom, and ring A represents an optionally substituted hydrocarbon aromatic ring. ) The guanine indicator according to claim 2 is characterized by using the spiropyridopyran compound according to claim 1.

The present invention will be described in detail below.

In the general formula [I], the alkyl group represented by R ¹ and R ² is an alkyl group having 1 to 7 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group and heptyl group. Group, and preferably a methyl group, an ethyl group or a propyl group.

The alkyl group which may have a substituent represented by R ³ is an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 1 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms.
Alkoxyalkyl groups such as alkyl groups of 2, 1 to 1 carbon atoms
An acyloxyalkyl group such as an alkyl group having 1 to 12 carbon atoms substituted with an acyloxy group such as an alkylcarbonyloxy group having 10 carbon atoms or a benzoyloxy group, and having 1 to 10 carbon atoms
1-12 carbon atoms substituted with the alkoxycarbonyl group of
Alkoxycarbonylalkyl groups such as alkyl groups, alkoxyalkoxyalkyl groups, and aralkyl groups represented by the following formulas and the like.

[0011]

[Chemical 3]

(In the formula, m represents an integer of 1 to 3, R ⁵ represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms.) R ⁴ has 1 to 10 carbon atoms in addition to a hydrogen atom. Alkyl group, an alkylcarbonyl group having 1 to 10 carbon atoms,
An acyl group such as a benzoyl group can be mentioned.

Examples of the hydrocarbon-based aromatic ring of ring A include a benzene ring and a naphthalene ring, and preferably a benzene ring. As a substituent of the aromatic ring of ring A, a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom; a nitro group; an alkyl group such as an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms And the like; alkoxycarbonyl groups such as alkoxycarbonyl groups having 1 to 6 carbon atoms; alkoxysulfonyl groups such as methoxysulfonyl group and ethoxysulfonyl group; and alkylsulfonyl groups such as methylsulfonyl group and ethylsulfonyl group.

The spiropyridopyran compound of the present invention represented by the above general formula [I] develops color by a guanine derivative, which is selected by guanine by hydrogen bond as in the following general formula [II]. This is the result of a positive recognition.

[0015]

[Chemical 4]

(R ¹ , R ² , R in the general formula [II]
³ , R ⁴ , X, Y and ring A have the same meaning as in general formula [I], and G has the same meaning as in general formula [III] below. The guanine derivative is not particularly limited as long as it contains a guanine group, and examples thereof include a guanine derivative represented by the following general formula [III].

[0017]

[Chemical 5]

(In the formula, G represents a hydrogen atom or a group represented by the following formula.)

[0019]

[Chemical 6]

(In the formula, R ⁶ is a hydrogen atom or --OSiMe.
₂ Indicates Bu (t). In addition, Me is a methyl group and Bu is a butyl group. ) The spiropyridopyran compound of the present invention represented by the above general formula [I] can be produced, for example, as follows. That is, it can be synthesized by reacting a compound represented by the following general formula [IV] with a compound represented by the following general formula [V].

[0021]

[Chemical 7]

(In the formula, R ¹ , R ² , R ³ and ring A have the same meaning as in the above formula [I], and X ⁻ represents a monovalent anion. 1 represented by X ⁻ Examples of valent anions include halogen ions such as chlorine ion, bromide ion, and iodo ion, perchlorate ion, and tetrafluoroborate ion.)

[0023]

[Chemical 8]

(In the formula, X, Y and R ⁴ have the same meanings as in the above formula [I].) This reaction is usually a halogenated hydrocarbon such as methylene chloride or chloroform, or methanol or ethanol. At a reaction temperature of -20
It is carried out at -100 ° C.

Specific examples of the spiropyridopyran compound of the present invention thus obtained are shown in Tables 1 and 2 below.

[0026]

[Table 1]

[0027]

[Table 2]

Such a spiropyridopyran compound of the present invention may be dissolved in a solvent together with a binder to form an ink composition, or it may be coated on an appropriate substrate and dried, depending on the application. Alternatively, it can be used by dissolving or dispersing it in a resin and then forming a film.

The solvent used in the ink composition containing the compound of the present invention is not particularly limited as long as it can dissolve the compound of the present invention.

As the resin for dissolving or dispersing the compound of the present invention, polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate,
Cellulose acetate, epoxy resin, phenol resin and the like can be mentioned. As a film forming method, various known methods can be adopted.

When the compound of the present invention is used after being dissolved or dispersed in a resin, an antioxidant and a singlet oxygen quencher may be added for the purpose of improving stability and light resistance.

The spiropyridopyran compound of the present invention is
It can be effectively used as a guanine indicator because it selectively recognizes a guanine derivative and develops color. In addition, by using this color development system, recording materials, memory materials, temperature indicating materials, etc. Can also be used as

[0033]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Table 1, No. 1 Preparation of Spiropyridopyran Compound of 1: (1) Synthesis of 6-acetylamino-3-cyano-2-acetyloxypyridine

[0035]

[Chemical 9]

6-amino-3-cyano-2-hydroxypyridine (P. Pojanagaroon, Ph. D. Thesis. Universi
ty of North Carolina, 1969) 20 mmol was suspended in acetic anhydride (Ac ₂ O) (30 ml) and the suspension was added at 120 ° C. for 12 hours.
Reacted for hours. After completion of the reaction, acetic anhydride was removed under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution; CH ₂ Cl ₂ : AcOEt (ethyl acetate) = 20: 1). Yield 70%.

Analysis result IR (KBr): 3250, 2230, 1790, 16
^{80,1520cm -1 1 H-NMR (270MHz} , CDCl 3): δ 2.
24 (s, 3H), 2.41 (s, 3H), 8.01
(D, J = 8.6 Hz, 1H), 8.27 (d, J =
8.6 Hz, 1 H) ¹³ C-NMR (67.5 MHz, CDCl ₃ ): δ 2
1.26, 25.26, 98.10, 111.86, 1
14.47, 145.46, 153.45, 158.2
4,168.04,169.17 MS (m / z): 219 (M ⁺ , 6%), 177 (M ⁺
_{-COCH 3 + H, 37%)} , 135 (M + -2COC
(H ₃ + 2H, 100%) (2) Synthesis of 6-acetylamino-3-cyano-2-hydroxypyridine

[0038]

[Chemical 10]

6-Acetylamino-3 obtained in (1)
10 mmol of cyano-2-acetyloxypyridine was added to MeOH: CH ₂ Cl ₂ : AcOH: H ₂ O (20: 2
It was dissolved in 0: 1: 1 (ml)) and stirred at room temperature for 25 hours. The target product was obtained by filtering the generated precipitate. Yield 94%.

Analysis result IR (KBr): 3430, 3100, 2210, 15
^{90,1560cm -1 1 H-NMR (270MHz} , DMSO-d 6): δ
2.15 (s, 3H), 6.89 (d, J = 8.2H
z, 1H), 7.84 (d, J = 8.2Hz, 1H),
11.01 (s, 1H), 12.15 (s, 1H) ¹³ C-NMR (67.5 MHz, DMSO-d ⁶ ): δ
24.40, 91.17, 96.38, 118.5
0, 147.43, 151.89, 166.53, 17
0.41 MS (m / z): 177 (M ⁺ , 20%), 135 (M
_{^{+ -COCH 3 + H, 100%}} ) (3) 6- Synthesis of acetyl-amino-3-formyl-2-hydroxypyridine [Va]

[0041]

[Chemical 11]

6-Acetylamino-3 obtained in (2)
-Cyano-2-hydroxypyridine (5.0 mmol)
And Raney Ni (W-6, 1.0 g) and sodium phosphinate monohydrate (1.7 g) in H ₂ O: AcOH: pyridine (6.3: 6.3: 12.5 (ml)). The suspension was suspended and stirred in an autoclave under a hydrogen pressure of 12 atm at room temperature for 24 hours. After the reaction was completed, the reaction mixture was filtered,
The filtrate was treated under reduced pressure to remove the solvent, and the residue was purified by silica gel column chromatography (developing solution;
CH ₂ Cl ₂ : EtOH = 20: 1). Yield 73%.

Analysis results IR (KBr): 3400, 3150, 2950, 16
^{90,1570cm -1 1 H-NMR (270MHz} , DMSO-d 6): δ
2.17 (s, 3H), 6.69 (d, J = 8.2H
z, 1H), 7.94 (d, J = 8.2Hz, 1H),
9.96 (s, 1H) ¹³ C-NMR (67.5 MHz, DMSO-d ⁶ ): δ
24.48, 96.14, 116.33, 143.6
0, 151.95, 162.61, 172.03, 18
7.67 MS (m / z): 180 (M ⁺ , 25%), 138 (M
_{^{+ -COCH 3 + H, 92%}} ) (4) Synthesis of Spiro pyrido pyran-based compounds [Ia]

[0044]

[Chemical formula 12]

6-Acetylamino-3 obtained in (3)
- In-formyl-2-hydroxypyridine [Va] (Formula [V], X = CH, Y = O, R 4 = COC
H ₃ ) 1.0 mmol and 1,2,3,3-tetramethylindolenium iodide [IVa] (the above-mentioned general formula [I
V], the ring A is a benzene ring, and R ¹ ═R ² ═R ³ ═C
H ₃ , X ⁻ = I ⁻ ) 1.1 mmol and CH ₂ Cl ₂
It was stirred in (7 ml) for 12 hours at room temperature. After completion of the reaction, 1.0% aqueous potassium carbonate solution (50 ml) was added, and the mixture was extracted several times with methylene chloride. The solvent was removed from the extract using a rotary evaporator, and the residue was purified by silica gel column chromatography (developing solution; hexane: AcOEt: Et ₃ N = 10: 10: 1). Yield 5
7%.

The analytical results ^{IR (KBr): 3400,3210,1730,1710cm -1 1} H-NMR (CDCl 3, 270MHz): δ 1.
18 (s, 3H), 1.32 (s, 3H), 2.10
(S, 3H), 2.75 (s, 3H), 5.69 (d,
J = 10.4 Hz, 1H), 6.51 (d, J = 7.5)
Hz, 1H), 6.80 (t-d, J = 7.5, 1.2)
Hz, 1H), 6.82 (d, J = 10.4Hz, 1
H), 7.04 (t-d, J = 7.5, 1.2 Hz, 1
H), 7.12 (t-d, J = 7.5, 1.2 Hz, 1
H), 7.40 (d, J = 7.9 Hz, 1H), 7.7
0 (d, J = 7.9 Hz, 1H), 7.77 (br.
s, 1H) ¹³ C-NMR (CDCl ₃ , 67.5 MHz): δ 2
0.40, 25.07, 26.44, 29.35, 5
2.33, 106.65, 107.64, 108.2
9, 110.49, 119.51, 120.01, 12
1.95, 128.06, 128.40, 136.7
1,137.64, 148.29, 149.85, 15
9.83, 168.83 MS (m / z): 335 (M ⁺ , 63%) Example 2 Coloring of spiropyridopyran compound [Ia] obtained in Example 1 by guanine derivative: in Example 1 The spiropyridopyran compound [Ia] 2.99 × 10 ⁻⁵ mol in methylene chloride solution was added to the following nucleoside derivatives [IIIG], [IIIC], [IIIA], and [IIIT] in a molar ratio of 10 times. ]
, [IIIU] was added and the UV-visible spectrum was measured. The result is shown in FIG. As a result, a strong red color was developed only when the nucleoside derivative [IIIG] having a guanine group was added. This is the result of the spiropyridopyran compound [Ia] selectively recognizing the guanine group of the nucleoside derivative [IIIG] and opening the ring as in the above general formula [II].

[0047]

[Chemical 13]

[IIIG]: B = guanine, R = OSiMe
₂ Bu (t) [IIIC]: B = cytosine, R = OSiMe ₂ Bu (t) [IIIA]: B = adenine, R = OSiMe ₂ Bu (t) [IIIT]: B = thymine, R = H [IIIU] ]: B = uracil, R = OSiMe ₂ Bu (t) Example 3 Inhibition of color development in Example 2 by cytosine derivative: Spiropyridopyran compound [Ia] and guanine derivative [IIIG] prepared in Example 2 The nucleoside derivatives [IIIU], [IIIT], [IIIA], and [IIIC] were added to the color-developing solution with the guanine derivative in a molar ratio of 3 times, and then the UV-visible absorption spectrum was measured. The results are shown in Figure 2.

As shown in FIG. 2, the nucleoside derivative
The color development (red) was inhibited only when [IIIC] was added. This is because guanine group and cytosine group are strong and Watso
This is because the spiropyridopyran-based compound [Ia] of the present invention and the spiropyridopyran-based compound [Ia] and the guanine derivative [IIIG] are cleaved by the n-Crick type complementary interaction. It shows that the guanine derivative [IIIG] was interacting by molecular recognition.

[0050]

INDUSTRIAL APPLICABILITY As described in detail above, the spiropyridopyran compound of the present invention is a novel substance and selectively recognizes a guanine derivative to develop a color, so that it is industrially used as a guanine indicator or the like. Extremely useful.

[Brief description of drawings]

FIG. 1 is an ultraviolet-visible spectrum diagram showing the results of Example 2.

FIG. 2 is an ultraviolet-visible spectrum diagram showing the results of Example 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07D 513/20 8415-4C

Claims (2)

[Claims] 1. A spiropyridopyran compound represented by the following general formula [I]: [Chemical 1] (In the formula, R ¹ and R ² represent an alkyl group, R ³ represents an alkyl group which may have a substituent, R ⁴ represents a hydrogen atom, an alkyl group or an acyl group, and = X- represents ═CH— or ═N—, Y represents an oxygen atom or a sulfur atom,
Ring A represents an optionally substituted hydrocarbon aromatic ring. ) 2. A guanine indicator characterized by using the spiropyridopyran compound according to claim 1.